Urea cross-linked polypeptides derived from gelatin for the treatment of human hair



United, States Patent )7 3,354,039 UREA CROSS-LINKED POLYPEPTIDES DERIVED FROM GELATIN FOR THE TREATMENT OF HUMAN HAIR Heinz Lukesch, Hamburg-Sasel, and Giinther Bechmann,

Hamburg-Altona, Germany, assignors to Hans Schwarzkopf, Hamburg-Altona, Germany No Drawing. Filed Jan. 7, 1964, Ser. No. 336,114 Claims priority, application Germany, Jan. 8, 1963, Sch 32,569 6 Claims. (Cl. 16787.1)

The present invention relates to the treatment of hair and, more particularly, the present invention is concerned withthe setting of living human hair.

- For setting hair, film-forming materials are used which are soluble in water or aqueous lower alcohols. In order to achieve the desired effect, it is important that the film which will be formed so as to at least partially and preferably completely cover individual hairs, will be of sufficient, i.e., relatively high, resiliency. This is important because brittle films or portions thereof would be dislocated and removed during combing and would form insoluble deposits on brush and comb and also on the hair itself where on these deposits would no longer be in the shape of the desired, substantially continuous film.

Hair setting agents which are applied to the moist hair prior to insertion of curlers or the like, and thus prior to drying and combing out, as well as hair setting agents which are sprayed or otherwise applied after combing and forming of the desired hairdo, should have the following properties:

(1) Good film-forming properties so that a strengthening film will be formed to cover the hair along its entire length.

(2) A relatively high degree of resiliency.

(3) Little hygroscopicity. .1'('4) Lustering properties, to give the hair the desired g oss. v a

(5) It should be possible to wash out the setting agent with conventional shampoos and the like.

(6) Physiological compatibility with the human hair and scalp.

Conventionally, the film-forming agents used for setting hair consist essentially of one or the other of the following'materialsz. shellac, alginate, carragenate, gelatin, dextrine, polyvinyl pyrrolidone and copolymerizates thereof with polyvinyl acetate, dimethylhydantoinformaldehyde resin and polymer acrylic acid derivatives.

The above-listed materials are partly of natural and partly of synthetic origin; however, they fulfill only-some of the requirements made on a hair-setting or strengthening-agent'.

Gelatin, being a natural product, has many advantages as a hair'setting agent. However, the gelatin film is'too brittle and thus of little resistance against wear and tear such as combing. This disadvantage cannot be overcome by the addition of softening agents since the latter are not suificiently compatible with gelatin. h

It is therefore an object of the present invention to overcome the above-discussed diificulties and disadvantages.- 7

It is a further object of the'present invention to provide a hair setting agent which will possess to a high degree the above enumerated desirable properties.

It is another object of the present invention to provide a method of producing such hair-treating agent.

It is yet a further object of the present invention to provide an advantageous method of treating hair.

Other objects and advantages of the present invention Patented Nov. 21, 1967 With the above and other objects in view, the present invention includes a hair treating agent consisting essentially of a carrier substance compatible with human hair, and having an effective amount, preferably between about 0.3% and 3%, of an urea cross-linked polypeptide derived from gelatin and having an average molecular weight of between about 20,000 and 60,000, preferably about 35,000, distributed therethrough.

The present invention also provides a mixture adapted to be sprayed from a pressure-container provided with a spray nozzle, the-mixture comprising a hair treating agent consisting essentially of a carrier substance compatible with human hair and having an effective amount of a urea cross-linked polypeptide derived from gelatin distributed therethrough, and a liquefied gas having at atmospheric pressure a boiling point below ambient temperatul'e.

The present invention is also concerned with a method of setting hair which includes the step of applying to living human haira hair-treating agent consisting essentially of a carrier substance.compatiblewith human hair and having an effective amount of a urea cross-linked polypeptide derived from gelatin distributed therethrough.

In addition, the present invention provides, in a method of producing a hair-treating agent adapted to set human hair, the steps of degrading gelatin so as to form polypeptides thereof, and reacting the polypeptides with a diisocyanate so'as to form urea cross-linked polypeptides having an average molecular weight of between about 20,000'and 60,000;

Surprisingly it has been found according to the present invention that by degrading gelatin to polypeptides and then cross-linking the thus-formed polypeptides with a diisocyan'ate to urea cross-linked polypeptides, preferably having an average molecular weight of about 35,000, a composition is formed which is outstandingly suitable for setting and strengthening hair. The advantageous properties which are already found in gelatin are maintained and additionally the .thus-formed composition possesses to a higher degree the properties enumerated further above...

For the sake of .brevity, the urea cross-linked polypeptides will be referred to herein as modified gelatin.

The advantageous properties of the modified gelatin formed. by reacting polypeptides with diisocyanates, as

' discussed above, may be due to the difference between will become apparent from a further reading of the de scription andof the appended claims.

the configuration of the molecules of regular gelatin, which are rod-shaped and thus give rigid structures, and the more globular configuration or shape of the molecules of the modified gelatin. Without limiting the present inventionto' any specific theoretical explanation, it seems likely that "the physical characteristics, such as film-forming properties, adherence and surface characteristics, of the modified gelatin are improved due to this difference in the shape of the molecules. Furthermore, due to' the globular character of the molecules of the modified gelatin, the same does 'not show the thixbtropic increase in viscosity which will be found in the case of gelatin.

The modified gelatin of the present invention may be incorporated .in hair-grooming preparations such .as creams, hair setting agents, hair lotions and the like. Particularly, hair setting compositions incorporating the modified gelatin of the present invention are preferably applied by spraying from a pressure containerby means of a propellant gas, such as a conventional aerosol container. The solvent for the modified gelatin as well as the propellant gas, of course, must be compatible with the modified gelatin.

It is also possible to combine the hair. treatingv agents of the present invention with other materials compatible therewith and having an independent favorable effect, such as materials which will make it easier to comb the hair, or Vitamins, lanolin, lanolin derivatives, perfumes and the like.

The following examples are given as illustrative only, without limiting the invention to the specific details of the examples.

Example I.-Hair grooming cream G. Modified gelatin 7 2.00 Sodium alginate 1.50 Water -7 i 80.00 Diethylene glycol h 0.15 Perfume 0.30 Isopropanol or ethanol 17.05

Example II.-Hair treating agent G. Modified gelatin 2.00 Dimethyl phthalate 0.50 Perfume 0.30 Isopropanol or ethanol 39.50 Water 57.70

Example III.Hair setting agent G. Modified gelatin 3.00 Alcohol-soluble lanolin derivative 0.05 Isopropanol or ethanol 25.00 Water L 45.00 Perfume 0.30 Isobutane or a mixture of 40 parts difiuorodichloromethane and 60 parts tetrafiuorodic-hloroethane 26.65

100.00 Example. I. Ve H air trea ing agent G. Cetyl alcohol 0.90 Glyeerine-monostearate 0.60 Benzyl-trimethylammonium chloride 0.20 p-Qxybenzoic acid methyl ester 0.03 Modified gelatin 1.10 Perfume 0.10 Water 97.07

100.00 Example V.-Hair treating lotion G. Sodium panthothenate 0.20 Inositol Polyglycol 200 0.25 Modified gelatin 0.45 Ethanol 50.00 Perfume 0.70 Water 48.30

Example Vl.- Prdacti0n of modified'gelatin 1 liter of a 5% aqueous solution of purified gelatin is adjusted to a pH of 6.9. This solution is heated for 5 /2 hours in a closed vessel within a steam pressure container to 120 C. The solution is cooled down to 90 C. and allowed to stand until room temperature is reached. The solution is then filtered and adjusted to a pH-value of,7.

To carry out the cross-linking of the polypeptides, a solution of 1.66 cc. hexamethylene-diisocyanate in 25 com. tetrahydrofurane is added under rigorous stirring, the temperature of the solutions being 30 C.

The pH-value of the solution is currently controlled and maintained at a value of 7, by adding diluted sodium lye. After 3 hours the reaction is complete. To remove the tetrahydrofurane, the solution is concentrated by vacuum distillation to half its volume, after addition of some drops of octyl alcohol to prevent foaming.

Now the solution is subjected to freeze drying. The resulting powder of modified gelatin can be used as described in the foregoing examples. In a similar manner further products of modified gelatin can be produced as described in the German Patent 1,118,792.

Below are given some characteristics of the modified gelatin for the purpose of the invention: (1) The minimum molecular Weight of the polypeptides is 10,000, the maximum 15,000, while the preferred molecular weight is 12,000. (2) In general, the polypeptides are produced by thermic hydrolysis of the aqueous solution of purified gelatin within the temperature range of 60-l50 C. (3) The-maximum and minimum weights of the urea crosslinked polypeptides are between 20,000 and 60,000. (4) If the number of the peptide chains in the cross-linked polypeptides is n, the number of the cross-linking diisocyanates is n-l. (5) The cross-linking of the polypeptides is carried out by reaction of the aqueous solution of the polypeptides with a tetrahydrofurane solution of a di-v isocyanate at a neutral pH and room temperature for a period of several hours.

Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can by applying current knowledge readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention and, therefore, such adaptations should and are intended to be comprehended within the meaning and range of equivalence of the following claims.

What is claimed as new and desired to. be secured by Letters Patent is:

1. A mixture adapted to be sprayed from a pressure container provided with a spray nozzle, said mixture comprising a hair treating agent consisting essentially of a carrier substance compatible with human hair and having between about 0.3% and 3% of urea cross-linked polypeptides derived from gelatin and having an average molecular weight of between about 20,000'and 60,000 distributed therethrough, and a liquefied gas having at atmospheric pressure a boiling point, below ambient temperature.

2. A mixture adapted to be sprayed from a pressure container provided with a spray nozzle. said mixture comprising a hair treating agent consisting, essentially of a carrier substance compatiblev with human hair and hav-v ing an effective amount of urea cross-linked polypeptides derived from gelatin and having an average. molecular weight of about 35,000 distributed therethrough, and a, liquefied gas having at atmospheric pressure a boiling point below ambient temperature.

3. A mixture adapted to be sprayed from. a pressure container provided with a spray nozzle, said mixture comprising a hair treating agent consisting essentially of a carrier substance compatible with human hair and having between about 0.3% and 3% of urea cross-linked polypeptides derived from gelatin and having an average molecular weight of about 35,000 distributed therethrough, and a liquefied gas having at atmosphericpres sure a boiling point below ambient temperature.

4. A mixture adapted to be sprayed from a pressure container provided with a spray nozzle, said mixture comprising a hair-treating agent consisting essentially of a carrier substance compatible with human hair, having an effective amount of urea cross-linked polypeptides derived from gelatin and having an average molecular weight of between about 20,000 and 60,000 distributed therethrough, and a liquefied gas having at atmospheric pressure a boiling point below ambient temperature.

having an average molecular weight of about 35,000 distributed therethrough.

References Cited UNITED STATES PATENTS 3,057,782 10/1962 Lindner et a1. 260-417 ALBERT T. MEYERS, Primary Examiner.

10 SAM ROSEN, Examiner.

V. C. CLARKE, Assistant Examiner. 

1. A MIXTURE ADAPTED TO BE SPRAYED FROM A PRESSURE CONTAINER PROVIDED WITH A SPRAY NOZZLE, SAID MIXTURE COMPRISING A HAIR TREATING AGENT CONSISTING ESSENTIALLY OF A CARRIER SUBSTANCE COMPATIBLE WITH HUMAN HAIR AND HAVING BETWEEN ABOUT 0.3% AND 3% OF UREA CROSS-LINKED POLYPEPTIDES DERIVED FROM GELATIN AND HAVING AN AVERAGE MOLECULAR WEIGHT OF BETWEEN ABOUT 20,000 AND 60,000 DISTRIBUTED THERETHROUGH, AND A LIQUEFIED GAS HAVING AT ATMOSPHERIC PRESSURE A BOILING POINT BELOW AMBIENT TEMPERATURE. 